Maltyl-2-methyl alkenoates and novel perfume compositions and perfumed articles containing same

ABSTRACT

Described are maltyl-2-methyl alkenoates having the structure: ##STR1## wherein R is an alkenyl moiety having one of the structures: ##STR2## AS WELL AS THE USES THEREOF IN PERFUMERY, THAT IS, PERFUME COMPOSITIONS AND PERFUMED ARTICLES AS WELL AS COLOGNES OF SAID COMPOUNDS.

BACKGROUND OF THE INVENTION

The present invention relates to maltyl-2-methyl alkenoates having thestructure: ##STR3## wherein R is an alkenyl moiety having one of thestructures: ##STR4## AND USES THEREOF TO AUGMENT OR ENHANCE THE AROMA OFPERFUME COMPOSITIONS, PERFUMED ARTICLES AND COLOGNES.

There has been considerable work performed relating to substances whichcan be used to augment or enhance or impart aromas to (or in) variousconsumable materials, such as perfume compositions, perfumed articlesand colognes. These substances are used to diminish the use of naturalmaterials, some of which may be in short supply and to provide moreuniform properties in the finished product. Sweet, fruity, jammy,pineapple-like, strawberry and green floral aromas and nuances aredesirable in perfume compositions, perfumed articles and colognes.

U.S. Pat. No. 4,000,327 issued on Dec. 28, 1976 discloses the use inperfume compositions and perfumed articles of esters of2-methyl-cis-3-pentenoic acid wherein the ester moiety is lower alkylhaving from 2 up to 6 carbon atoms.

British Pat. No. 1,379,038 published on Jan. 2, 1975 includes a broaddisclosure of γ,δ-unsaturated carbonyl compounds, useful as flavoringand odoriferous agents of the formula: ##STR5## (where m is 0 or 1; n=0and the dotted line is a bond or n=1 and the dotted line is no bond; R¹,R², R³, R⁴, R⁵, R⁶ and R⁷ are each H, or linear or branched (a) cyclic,(un)saturated univalent hydrocarbon or oxygen-substituted hydrocarbon;or R⁷ with R³ or R⁴ or R⁵ may form a cycloaliphatic group, provided thatR³ and R⁵ may not contain a multiple bond which is conjugated with thealpha, beta-bond) as being prepared by reacting analpha-beta-unsaturated carbonyl compound (R⁵)(R³)_(n) C═C(C)--(O)_(m)--R⁷ or halogenated carbonyl compound X(R⁵)(R³)_(n) --CH(R⁴)_(n)--C(O)--R⁷ with an organometallic compound comprising a transition metal(preferred: Cu), an univalent cation (preferred: Li⁺) or [Mg-HALOGEN]⁺and an alkenyl radical R⁶ --C(R¹)═C(R²)--, preferred in the presence ofa complexing agent, e.g., diethyl ether, tetrahydrofuran,dimethoxyethane, N-tributylphosphine or trimethylphosphite.

Maltol itself having the structure: ##STR6## is described by Arctander,"Perfume and Flavor Chemicals (Aroma Chemicals)" at number 1831 as beinguseful in perfumery.

However, nothing set forth in the above-mentioned prior art or in anyother pertinent prior art discloses novel compounds of our inventionwith structures even remotely similar to the novel compounds of ourinvention. Furthermore, nothing in the prior art discloses theproperties of the compounds of our invention that are unobvious andadvantageous in the field of alkenoic acid esters.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 represents the GLC profile for the reaction product of Example I,which is maltyl-2-methyl-3-pentenoate having a high proportion (greaterthan 50%) of maltyl-2-methyl-cis-3-pentenoate.

FIG. 2 represents the NMR spectrum for maltyl-2-methyl-3-pentenoateproduced according to Example I.

FIG. 3 represents the Infrared spectrum for the reaction product ofExample I, which is maltyl-2-methyl-3-pentenoate.

FIG. 4 represents the GLC profile for the reaction product of ExampleII, which is maltyl-2-methyl-2-pentenoate.

FIG. 5 represents the NMR spectrum for the reaction product of ExampleII, which is maltyl-2-methyl-2-pentenoate.

FIG. 6 represents the Infrared spectrum for the reaction product ofExample II, which is maltyl-2-methyl-2-pentenoate.

FIG. 7 represents the GLC profile for the reaction product of ExampleIII, which is maltyl tiglate.

FIG. 8 represents the NMR spectrum for the reaction product of ExampleIII, which is maltyl tiglate.

THE INVENTION

It has now been discovered that solid and liquid perfume compositions,perfumed articles, including soaps, detergents and cosmetic powders andcolognes having sweet fresh strawbery/pineapple, sweet, fruity, jammyaromas with green floral nuances may be provided by the utilization ofcompositions of matter containing one or more maltyl-2-methyl alkenoateshaving the structure: ##STR7## wherein R is one of the moieties:##STR8##

Thus, for example, maltyl-2-methyl-3-pentenoate (having the C.A.S. name3-hydroxy-2-methyl-4H-pyran-4-one-2-methyl-3-pentenoate) having thestructures: ##STR9## has a sweet fresh strawberry/pineapple aroma withgreen and floral nuances.

Maltyl tiglate (having the C.A.S. name 3-hydroxy-2-methyl-4H-pyran-4-onetiglate) and the structure: ##STR10## at 1% in food grade ethanol, has asweet, fruity, jammy, pineapple, strawberry-like aroma.

The maltyl-2-methyl alkenoates of our invention are capable of beingformed by first reacting appropriate acid, e.g., tiglic acid or2-methyl-3-pentenoic acid with a thionyl halide, e.g., thionyl chloride(SOCl₂); then reacting the thus formed acyl halide with maltol therebyproducing the maltyl-2-methyl alkenoate which is then subsequently usedin perfume compositions, perfumed articles and colognes. Theafore-described reaction is illustrated as follows: ##STR11##

2-Methyl-3-pentenoic acid is produced according to the processes setforth in U.S. Pat. No. 3,984,579 issued on Oct. 5, 1976.

Thus, for example, Example XIV sets forth a method for the preparationof 2-methyl-cis-3-pentenoic acid having a purity of greater than 99%.Example I of U.S. Pat. No. 3,984,579 sets forth a method for producing acis:trans mixture of 2-methyl-3-pentenoic acid wherein the cis:transratio is 60:40. Any of the mixtures of isomers of 2-methyl-3-pentenoicacid produced according to the processes set forth in U.S. Pat. No.3,984,579 may be used for the purposes of producing the maltyl-2-methylalkenoates of the instant invention.

One or more maltyl-2-methyl alkenoates and an auxiliary perfumeingredient including, for example, alcohols, aldehydes, nitriles, estersother than the maltyl-2-methyl alkenoates of our invention, cyclicesters (lactones) and natural essential oils may be admixed with themaltyl-2-methyl alkenoates of our invention so that the combined odorsof the individual components produce a pleasant and desired fragrance,particularly and preferably in strawberry fragrances. Such perfumecompositions usually contain (a) the main note or the bouquet orfoundation stone of the composition; (b) modifiers which round off andaccompany the main note; (c) fixatives which include odorous substanceswhich lend a particular note to the perfume throughout all stages ofevaporation and substances which retard evaporation; and (d) topnoteswhich are usually low boiling fresh smelling materials.

In perfume compositions, the individual components will contribute itsparticular olfactory characteristics, but the over-all effect of theperfume composition will be the sum of the effects of each of theingredients. Thus, one or more of the maltyl-2-methyl alkenoates can beused to alter the aroma characteristic of a perfume composition, forexample, by utilizing or moderating the olfactory reaction contributedby another ingredient in the composition.

The amount of maltyl-2-methyl alkenoates of our invention which will beeffective in perfume compositions depends on many factors, including theother ingredients, their amounts and the effects which are desired. Ithas been found that perfume compositions containing as little as 0.3% ofmaltyl-2-methyl alkenoates or even less (e.g., 0.05%) can be used toimpart a scent odor to soaps, cosmetics or other products. The amountemployed can range up to 5% of the fragrance components and will dependon considerations of cost, nature of the end product, the effect desiredon the finished product and the particular fragrance sought.

The maltyl-2-methyl alkenoates are useful in perfume compositions as anolfactory component in detergents and soaps, space odorants anddeodorants, perfumes, colognes, toilet waters, bath preparations, suchas bath oils, and bath solids; hair preparations, such as lacquers,brilliantines, pomades and shampoos; cosmetic preparations, such ascreams, deodorants, hand lotions and sun screens; powders, such astalcs, dusting powders, face powders and the like. When used as anolfactory component of a perfumed article, as little as 100 parts permillion of maltyl-2-methyl alkenoates will suffice to impart a fruity,acrid, strawberry character which is one of the key odor characteristicsof strawberry perfume formulations. Generally, no more than 2.0% of oneor more maltyl-2-methyl alkenoates based on the ultimate end product isrequired in the perfume composition.

In addition, the perfume composition or fragrance composition of ourinvention can contain a vehicle, or carrier for the maltyl-2-methylalkenoates. The vehicle can be a liquid such as an alcohol, a non-toxicalcohol, a non-toxic glycol, or the like. The carrier can also be anabsorbent solid, such as a gum (e.g., gum arabic) or components forencapsulating the composition (such as gelatin).

The following Examples are given to illustrate embodiments of theinvention as it is presently preferred to practice it. It will beunderstood that these Examples are illustrative and the invention is notto be considered restricted thereto except as indicated in the appendedclaims.

EXAMPLE I Preparation of Maltyl-2-Methyl-cis-3-Pentenoate Mixture##STR12## Procedure:

Into a 250 ml two necked reaction flask equipped with mechanicalstirrer, Fredrich's condenser and gas trap, 12 g of a mixture containinga high proportion of 2-methyl-cis-3-pentenoic acid prepared according toExample VII at column 18 of U.S Pat. No. 3,984,579 issued on Oct. 5,1976, in 50 ml benzene is added. Fredrich's condenser side arm isequipped in such a way as to vent the gases released through a trap intoa beaker containing commercial preparation of sodium hypochlorite(Clorox®). With vigorous stirring, 11.9 grams of freshly distilledthionyl chloride are added to the reaction mixture. The reaction mixtureis then stirred and heated until no more hydrogen chloride or sulfurdioxide gas is released (over a period of 45 minutes). The reaction massis then allowed to cool and 12.6 grams of maltol and 50 ml of benzeneare added thereto. The mixture is again heated until no more gas evolves(period of time: 45 minutes). The benzene solvent is then removed on arotary evaporator. The resulting reaction product,maltyl-2-methyl-3-pentenoate containing a high proportion (80%) ofmaltyl-2-methyl-cis-3-pentenoate and 20%maltyl-2-methyl-trans-3-pentenoate is trapped on a preparative GLCcolumn. Conditions: 12'×3/8" 20% SE-52 column programmed at 100°-190° C.at 8° C. per minute.

A total of 0.55 grams of maltyl-2-methyl-3-pentenoate is collectedhaving a purity of greater than 99%.

The GLC profile for the reaction product is set forth in FIG. 1. The NMRspectrum is set forth in FIG. 2. The Infrared spectrum formaltyl-2-methyl-3-pentenoate is set forth in FIG. 3.

EXAMPLE II Preparation of Maltyl-2-Methyl-2-Pentenoate ##STR13##Procedure:

119 Grams of thionyl chloride is distilled immediately before using(75°-76° C. at 760 mm pressure). While the thionyl chloride is beingdistilled, 114 grams of 2-methyl-2-pentenoic acid (mixture of cis andtrans isomers prepared according to the procedure of U.S. Pat. No.3,499,769 issued on Mar. 10, 1970) is melted using warm water. Themelted 2-methyl-2-pentenoic acid and distilled thionyl chloride are thenslowly added to a 1 liter three necked round bottomed flask equippedwith a mechanical stirrer and a Fredrich's condenser, the side arm ofwhich is equipped with a trap to vent the gas released into a beaker of5% sodium carbonate. The mixture is stirred and heated for a period of 1hour. The mixture is then cooled and maltol (126 grams) dissolved in 200cc of benzene is added. The reaction mass is then heated to reflux andstirred for a period of two hours. After cooling, the reaction mass isfiltered to recover a maltol precipitate. The supernatant liquid is thenadded to a separatory funnel and extracted with three volumes of 5%sodium carbonate. The supernatant liquid is then washed with water. Thebenzene is then removed using a rotary evaporator and the resultingproduct is recrystallized from ethyl acetate. The sodium carbonate layeris acidified with 2 molar aqueous hydrochloric acid and extracted with10% volumes of diethyl ether; then washed with water and dried overanhydrous sodium sulfate; then concentrated to 3.60 grams of residue.This residue is determined to be 2-methyl-2-pentenoic acid.

The recrystallization product from ethyl acetate weighs 30.62 grams andis identified as maltyl-2-methyl-2-pentenoate having a purity of 99.46%(yield: 13.8%).

The GLC profile for the reaction product containingmaltyl-2-methyl-2-pentenoate is set forth in FIG. 4. The NMR spectrumfor maltyl-2-methyl-2-pentenoate is set forth in FIG. 5. The Infraredspectrum for maltyl-2-methyl-2-pentenoate is set forth in FIG. 6.

EXAMPLE III Preparation of Maltyl Tiglate ##STR14## Procedure:

10 Grams of tiglic acid dissolved in 50 ml anhydrous benzene are placedin a 250 ml two necked reaction flask equipped with mechanical stirrerand Fredrich's condenser, whose side arm is equipped in such a way as tovent the gases released during the reaction through a trap and into abeaker containing a solution of sodium hypochlorite (Clorox®). 11.9Grams of thionyl chloride (freshly distilled) are added to the reactionmass. The mixture is then stirred and heated until no additionalhydrogen chloride or sulfur dioxide is released (period: 60 minutes).The reaction mass is then allowed to cool and 12.6 grams of maltol and50 cc of benzene are added. The reaction mass is then heated to refluxuntil no more sulfur dioxide or hydrogen chloride gas is released(period: 1 hour). The benzene is removed on a rotary evaporator.

The reaction mass solidifies upon refrigeration and is then dissolved inethyl acetate and placed in a freezer. The resultant crystals arefiltered and washed with ethyl acetate. The material is then purified byrecrystallization from ethyl acetate and a 96.9% pure material isobtained. This material is maltyl tiglate.

The GLC profile for the reaction product is set forth in FIG. 7. The NMRspectrum for maltyl tiglate is set forth in FIG. 8.

EXAMPLE IV Strawberry Fragrance

The following mixture is prepared:

    ______________________________________                                        Ingredient             Parts by Weight                                        ______________________________________                                        Cuminic acetate        15                                                     Ethyl acetoacetate     3                                                      Ethyl laurate          30                                                     Cinnamyl isobutyrate   15                                                     Cinnamyl decylate      20                                                     Diacetyl (10% in 95% aqueous                                                   ethanol)              2                                                      Ethyl pelargonate      5                                                      Gamma undecalactone    20                                                     Ethyl isobutyrate      110                                                    Ethyl isovalerate      60                                                     Ethyl heptanoate       12                                                     Dulcinyl               5                                                      2(para-hydroxyphenyl)-3-butanone                                                                     2                                                      Ethyl acetate          5                                                      Beta-ionone            5                                                      Palatone               3                                                      Vanillin               10                                                     Ethyl vanillin         10                                                     Ethyl-3-methyl-3-phenyl glycidate                                                                    70                                                     Maltyl-2-methyl-3-pentenoate                                                   prepared according to the                                                     process of Example I  10                                                     ______________________________________                                    

The mixture containing the maltyl-2-methyl-3-pentenoate preparedaccording to the process of Example I imparts the berry undertonenecessary to complete and round out the strawberry aroma.

EXAMPLE V Preparation of Maltyl-2-Methyl-cis-3-Pentenoate ##STR15##

Thionyl chloride is immediately distilled before use (76° at 760 mmpressure) and added to 2-methyl-cis-3-pentenoic acid prepared accordingto Example XIV at column 30 of U.S. Pat. No. 3,984,579 issued on Oct. 5,1976. A 1 liter three necked round bottomed flask equipped with aFredrich's condenser, mechanical stirrer and heating mantle is then usedfor the reaction. The mixture of 2-methyl-cis-3-pentenoic acid andthionyl chloride is stirred and heated for a period of 1.5 hours (untilno more sulfur dioxide or hydrogen chloride gas is emitted). A trap isthen connected to the side arm of the Fredrich's condenser and ventedinto a beaker containing a 5% solution of sodium bicarbonate to trap theevolved hydrogen chloride and sulfur dioxide. The mixture is thenallowed to cool to room temperature and 126 grams of maltol in 200 cc ofbenzene is added. The reaction mass is then heated to reflux for aperiod of one hour and then cooled. The unreacted 2-methyl-cis-3-pentenoic acid is extracted with 10 equal volumes of 5% sodiumcarbonate. The resulting reaction product is then washed with water. Theresulting mixture is then filtered and the solid is determined to beunreacted maltol (27.44 grams or 44.76%). The benzene is then removedfrom the supernatant liquid by means of a rotary evaporator, gaschromatography indicating that there remains some2-methyl-cis-3-pentenoic acid and benzene. The resulting product waspurified by means of vacuum distillation whereby the benzene and2-methyl-cis-3-pentenoic acid are removed. The impurities are distilledoff at 4 mm Hg pressure at 70°-80° C. The maltyl-2-cis-3-pentenoateresulting is greater than 99% pure. Yield=114.01 grams or 51.36%.

The sodium carbonate layer is acidified with 2 molar hydrochloric acidand extracted with three 10% volumes of diethyl ether and concentratedto yield 18.9 grams of 34.08% residual 2-methyl-3-pentenoic acid.

GLC, NMR, IR and Mass Spectral data indicate that the material ismaltyl-2-methyl-cis-3-pentenoate.

EXAMPLE VI Strawberry Fragrance

The following mixture is prepared:

    ______________________________________                                        Ingredient             Parts by Weight                                        ______________________________________                                        Cuminic acetate        15                                                     Ethyl acetoacetate     3                                                      Ethyl laurate          30                                                     Cinnamyl isobutyrate   15                                                     Cinnamyl decylate      20                                                     Diacetyl (10% in 95% aqueous                                                   ethanol)              2                                                      Ethyl pelargonate      5                                                      Gamma undecalactone    20                                                     Ethyl isobutyrate      110                                                    Ethyl isovalerate      60                                                     Ethyl heptanoate       12                                                     Dulcinyl               5                                                      2(para-hydroxyphenyl)-3-butanone                                                                     2                                                      Ethyl acetate          5                                                      Beta-ionone            5                                                      Palatone               3                                                      Vanillin               10                                                     Ethyl vanillin         10                                                     Ethyl-3-methyl-3-phenyl glycidate                                                                    70                                                     Maltyl tiglate prepared according                                              to the process of Example III                                                                       10                                                     ______________________________________                                    

The mixture containing maltyl tiglate prepared according to the processof Example III imparts a fruity, jammy, pineapple, strawberry undertoneto this perfume formulation thereby completing and rounding out thestrawberry fragrance thereof.

EXAMPLE VII Preparation of Soap Composition

One hundred grams of soap chips are mixed with one gram of the perfumecomposition of Example IV until a substantially homogeneous compositionis obtained. The perfumed soap composition manifests an excellentstrawberry character with a berry undertone.

EXAMPLE VIII Preparation of a Detergent Composition

A total of 100 g of a detergent powder is mixed with 0.15 g of theperfume composition of Example IV until a substantially homogeneouscomposition is obtained. This composition has an excellent strawberryfragrance.

EXAMPLE IX Preparation of a Cosmetic Powder Composition

A cosmetic powder is prepared by mixing in a ball mill, 100 g of talcumpowder with 0.25 g of the maltyl-2-methyl-3-pentenoate producedaccording to Example V. It has an excellent sweet freshstrawberry/pineapple aroma with green floral nuances.

EXAMPLE X Perfumed Liquid Detergent

Concentrated liquid detergents with a fruity, strawberry odor areprepared containing 0.10%, 0.15% and 0.20% of maltyl tiglate preparedaccording to Example III. They are prepared by adding and homogeneouslymixing the appropriate quantity of maltyl tiglate in the liquiddetergent. The detergents all possess a sweet fruity, jammy, pineapple,strawberry aroma, the intensity increasing with greater concentrationsof maltyl tiglate.

EXAMPLE XI Preparation of a Cologne and Handkerchief Perfume

The composition of Example IV is incorporated in a cologne at aconcentration of 2.5% in 85% aqueous ethanol; and into a handkerchiefperfume at a concentration of 20% (in 95% aqueous ethanol). The use ofthe mixture containing maltyl-2-methyl-3-pentenoate in the compositionof Example IV affords a distinct and definite strong strawberry aromawith a fruity note to the handkerchief perfume and cologne.

EXAMPLE XII Preparation of Soap Composition

One hundred grams of soap chips are mixed with 1 gram of maltyl tiglateproduced according to Example III until a substantially homogeneouscomposition is obtained. The perfumed soap composition manifests anexcellent sweet fruity, jammy, pineapple, strawberry aroma.

EXAMPLE XIII Preparation of a Detergent Composition

A total of 100 g of a detergent powder is mixed with 0.15 g of themixture containing maltyl tiglate produced according to Example IIIuntil a substantially homogeneous composition is obtained. Thiscomposition has an excellent strawberry aroma with a fruity note.

What is claimed is:
 1. Maltyl tiglate having the structure: ##STR16##